Two related methods are proposed for the general synthesis of complex polynuclear aromatic hydrocarbons. One method involves the cycloaddition of an aryne with 4-acylamino-1,2,4-triazole and the subsequent cycloaddition of a second aryne with the resulting N- aminoisoindole. The second method involves the conversion of 7- azabenzonorbornadienes to isoindoles, using an s-tetrazine derivative, followed by an aryne cycloaddition. In both methods the resulting 7- azadiarylnorbornadienes are converted to the fully aromatic hydrocarbon by removal of the nitrogen bridge. The net result is the "coupling" of two simple aromatic systems to form a complex aromatic system, the "coupling agent" having become a benzene ring. These proposed methods are directed at the syntheses of 1) Linearly annellated benzenes such as tetracene, heptacene, and octacene; 2) Selected carcinogenic polynuclear aromatic hydrocarbons; and 3) Anthracenes of unusual substitution. These aromatics are important in chemical carcinogenesis studies, crystal photoconductivity measurements, and magnetic property studies.